US3404074A - Iron plating method and composition - Google Patents
Iron plating method and composition Download PDFInfo
- Publication number
- US3404074A US3404074A US437276A US43727665A US3404074A US 3404074 A US3404074 A US 3404074A US 437276 A US437276 A US 437276A US 43727665 A US43727665 A US 43727665A US 3404074 A US3404074 A US 3404074A
- Authority
- US
- United States
- Prior art keywords
- iron
- bath
- sulfonic acid
- iron plating
- plating
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title description 96
- 229910052742 iron Inorganic materials 0.000 title description 48
- 238000007747 plating Methods 0.000 title description 32
- 238000000034 method Methods 0.000 title description 6
- 239000000203 mixture Substances 0.000 title description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 18
- 239000003795 chemical substances by application Substances 0.000 description 14
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 12
- 229960004887 ferric hydroxide Drugs 0.000 description 12
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 12
- 125000001624 naphthyl group Chemical group 0.000 description 9
- 125000000542 sulfonic acid group Chemical group 0.000 description 9
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 8
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 8
- 125000001931 aliphatic group Chemical group 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- 229910001447 ferric ion Inorganic materials 0.000 description 8
- 238000000151 deposition Methods 0.000 description 7
- 230000008021 deposition Effects 0.000 description 7
- 229960002089 ferrous chloride Drugs 0.000 description 7
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- 230000000996 additive effect Effects 0.000 description 6
- 229910052783 alkali metal Inorganic materials 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- -1 alkali metal salt Chemical class 0.000 description 5
- 239000002270 dispersing agent Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000002659 electrodeposit Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 3
- 238000009713 electroplating Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 159000000000 sodium salts Chemical class 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 150000001340 alkali metals Chemical group 0.000 description 2
- 239000007859 condensation product Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 229910001448 ferrous ion Inorganic materials 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Inorganic materials [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- XWROUVVQGRRRMF-UHFFFAOYSA-N F.O[N+]([O-])=O Chemical compound F.O[N+]([O-])=O XWROUVVQGRRRMF-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- LEKPFOXEZRZPGW-UHFFFAOYSA-N copper;dicyanide Chemical compound [Cu+2].N#[C-].N#[C-] LEKPFOXEZRZPGW-UHFFFAOYSA-N 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- SQZYOZWYVFYNFV-UHFFFAOYSA-L iron(2+);disulfamate Chemical compound [Fe+2].NS([O-])(=O)=O.NS([O-])(=O)=O SQZYOZWYVFYNFV-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- DGVVJWXRCWCCOD-UHFFFAOYSA-N naphthalene;hydrate Chemical compound O.C1=CC=CC2=CC=CC=C21 DGVVJWXRCWCCOD-UHFFFAOYSA-N 0.000 description 1
- 150000002790 naphthalenes Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000005185 salting out Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/20—Electroplating: Baths therefor from solutions of iron
Definitions
- the antipitting agent is a condensate of an aromatic sulfonic acid with an aldehyde in which the condensate has the general graphical formula (ARA')SO M, wherein R is an aliphatic nucleus, A and A designate aromatic groups containing naphthalene rings joined to the aliphatic nucleus, and 50 M designates at least one free sulfonic acid group in combination with a water-soluble, compound-forming radical M.
- ARA' general graphical formula
- This invention relates to the electrodeposition of iron and more specifically to an antipitting agent for an iron plating bath.
- ferric ion produce ferric hydroxide particles which adhere to the surface of the workpiece and provide sites upon which hydrogen can collect to prevent iron deposition. Continued de position on surrounding areas results in a pit in the surface of the iron deposit. If the ferric hydroxide deposits directly onto the basis metal, deposition may never occur there, so as to actually produce a hole in the resulting electrodeposit.
- an object of the present invention to provide an additive for iron plating baths which prevents pitting from occurring. It is also an object of this invention to provide a dispersant for ferric hydroxide in aqueous media. A further object is to provide an improved method for making iron plated articles.
- the invention comprehends electrodepositing an iron coating from an aqueous iron electroplating bath having an alkali metal salt of a condensed mono-naphthalene sulfonic acid.
- This salt disperses the ferric hydroxide normally produced during operation of the bath to prevent pitting in the iron deposit. While I have found that dispersing ferric hydroxide in the iron plating bath is a very effective means for reducing pitting, the usual dispersants simply are not satisfactory.
- the only antipitting agent which I have found that satisfactorily serves this purpose is a condensation product of an aromatic sulfonic acid from the naphthalene series and an aldehyde.
- a and A designate two or more aromatic groups, which may or may not be alike, that contain naphthalene rings joined to an aliphatic nucleus R.
- the aliphatic nucleus R can be one alkyl group, or a plurality of straight chain or branched alkyl groups.
- the M designates at least one free sulfonic acid group in combination with a water-soluble, compound-forming radical.
- the radical is preferably an alkali metal ion, or even a hydrogen ion.
- My antipitting agent is also commercially available from several sources under various trade names. It is available under the name Eloxan salt. It can also be obtained under the name Blancol N. It can also be obtained under the name Lomar PW. These commercially available materials can be directly used as purchased.
- Ferric hydroxide is an impurity norm-ally present in iron plating baths formulated with ferrous salts. It is generated principally due to atmospheric oxidation of the ferrous ions to the ferric state. This oxidation is accelerated by the high temperature at which these baths are use-d.
- the reduction in the hard iron deposition temperature is even more pronounced.
- the usual deposition temperature for producing hard iron deposits was about 160 F. to 170 F. With my additive I can produce hard iron deposits as low as 140 F.
- my additive disperses the ferric hydroxide present and consistently completely eliminates pitting in soft iron deposits. Moreover, it usually completely eliminates pitting in hard deposits, and at least materially reduces it in all cases.
- My antipitting agent has been found to be particularly beneficial in iron plating baths used to produce wearresistant iron coatings on aluminum surfaces, such as the wear surfaces of aluminum pistons.
- iron plating baths used to produce wearresistant iron coatings on aluminum surfaces, such as the wear surfaces of aluminum pistons.
- a cathodic current density of approximately 100-125 amperes per square foot can be used to deposit a hard iron coating. If one desires to protect the iron deposit for storage and the like, a thin tin coating can be applied. In such instance, one would rinse the part after iron plating, dip it in dilute hydrochloric acid, rinse again and then immerse it in a tin electroplating bath.
- the usual alkaline potassium stannate-potassium hydroxide electroplating bath can be used.
- An iron plating bath comprising an acid aqueous solution containing a ferrous iron salt and at least about 0.25 gram per liter of a water-soluble salt of an alkyl condensed naphthalene sulfonic acid having a general graphical formula (AR-A)SO M, wherein R is an aliphatic nucleus, A and A designate naphthalene rings joined to the aliphatic nucleus, and $0 M designates at least one free sulfonic acid group in combination with a water-soluble, compound-forming radical M.
- AR-A general graphical formula
- An iron plating bath comprising an acid aqueous solution containing a ferrous iron salt and at least about 0.25 gram per liter of the sodium salt of a formaldehyde condensed mono-naphthalene sulfonic acid having a general graphical formula (AR-A)SO M, wherein R is -CH A and A designate naphthalene rings joined to -CH and M designates at least one free sulfonic acid group wherein M is Na.
- AR-A general graphical formula
- An iron plating bath comprising an acid aqueous solution containing a ferrous iron salt and, as a pit preventative, from small but effective amounts up to about 7.5 grams per liter of a water-soluble alkali metal salt of the condensation product of a sulfonic acid from the paththalene series and formaldehyde, said condensate having a general graphical formula (AR-A)SO M, wherein R is -CH A and A designate naphthalene rings joined to CH and $0 M designates at least one free sulfonic acid group wherein M is alkali metal.
- AR-A general graphical formula
- An aqueous iron plating bath containing at least about 25 ounces per gallon ferrous chloride, at least 0.05%, by volume, free hydrochloric acid, at least about 0.25 gram per liter of an aromatic sulfonic acid-aldehyde condensate having the general graphical formula wherein R is an aliphatic nucleus, A and A designate aromatic groups containing naphthalene rings joined to the aliphatic nucleus, and $0 M designates at least one free sulfonic acid group in combination with a watersoluble, compound-forming radical M.
- An iron plating bath comprising at least about 25 ounces per gallon ferrous chloride, at least 0.05% by volume, free hydrochloric acid, about 0.5-1.0 gram per liter of a soluble condensate of mono-naphthalene sulfonic acid and formaldehyde, and water, said condensate having a general graphical formula (ARA)SO M, wherein R is CH A and A designate naphthalene rings joined to -CH and $0 M designates at least one free sulfonic acid group in combination with a Watersoluble, compound-forming radical M.
- ARA general graphical formula
- the method of iron plating which comprises immersing a metal part in an iron plating bath comprising an acidified aqueous solution containing a ferrous iron salt and at least about 0.25 gram per liter of the alkali metal salt of the condensate of mono-naphthalene sulfonic acid and formaldehyde, and applying a negative potential to the part immersed in said bath to electrodeposit iron thereon, said condensate having a general graphical formula (A--R-A')SO M, wherein R is --CH A and A designate naphthalene rings joined to -CH and $0 M designates at least one free sulfonic acid group wherein M is alkali metal.
- the method of making an improved wear-resistant coating on an aluminum piston which comprises preparing the aluminum surface for iron deposition, immersing the part while under a negative potential in an iron plating bath containing about 62-6 6 ounces per gallon of ferric chloride, about 0.2%-0.4%, by volume, free hydrochloric acid, about 0.5-1.0 gram per liter of sodium salt of a formaldehyde condensed mono-naphthalene sulfonic acid, and water, said condensate having a general graphical formula (AR-A')SO M, wherein R is CH A and A designate naphthalene rings joined to --CH and SO M designates at least one free sulfonic acid group wherein M is Na, said bath being at a temperature of about F.
- AR-A' graphical formula
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating And Plating Baths Therefor (AREA)
- Electroplating Methods And Accessories (AREA)
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US437276A US3404074A (en) | 1965-03-04 | 1965-03-04 | Iron plating method and composition |
| GB6959/66A GB1061950A (en) | 1965-03-04 | 1966-02-17 | Iron plating bath liquids and methods |
| FR51451A FR1470250A (fr) | 1965-03-04 | 1966-03-01 | Dépôt métallique anti-piqûre |
| DEG46190A DE1258697B (de) | 1965-03-04 | 1966-03-02 | Bad zum galvanischen Abscheiden von Eisenueberzuegen |
| BE706849D BE706849A (cg-RX-API-DMAC7.html) | 1965-03-04 | 1967-11-21 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US437276A US3404074A (en) | 1965-03-04 | 1965-03-04 | Iron plating method and composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3404074A true US3404074A (en) | 1968-10-01 |
Family
ID=23735784
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US437276A Expired - Lifetime US3404074A (en) | 1965-03-04 | 1965-03-04 | Iron plating method and composition |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US3404074A (cg-RX-API-DMAC7.html) |
| BE (1) | BE706849A (cg-RX-API-DMAC7.html) |
| DE (1) | DE1258697B (cg-RX-API-DMAC7.html) |
| GB (1) | GB1061950A (cg-RX-API-DMAC7.html) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4221639A (en) * | 1978-10-09 | 1980-09-09 | Kioritz Corporation | Aluminium alloy cylinder and manufacturing method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1441468A (en) * | 1918-08-12 | 1923-01-09 | Wills Child Harold | Composite metal structure for internal-combustion engines and method of forming the same |
| US2046758A (en) * | 1932-11-28 | 1936-07-07 | Dewey And Almy Chem Comp | Aqueous dispersion of carbon black |
| US2199806A (en) * | 1940-05-07 | Wetting | ||
| US3067243A (en) * | 1959-07-28 | 1962-12-04 | Nopco Chem Co | Preparation of salts of naphthalene sulfonic acid-formaldehyde condensates |
| US3193575A (en) * | 1961-03-10 | 1965-07-06 | Basf Ag | Production of condensation products of naphthalenesulfonic acids and aldehydes |
-
1965
- 1965-03-04 US US437276A patent/US3404074A/en not_active Expired - Lifetime
-
1966
- 1966-02-17 GB GB6959/66A patent/GB1061950A/en not_active Expired
- 1966-03-02 DE DEG46190A patent/DE1258697B/de active Pending
-
1967
- 1967-11-21 BE BE706849D patent/BE706849A/xx unknown
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2199806A (en) * | 1940-05-07 | Wetting | ||
| US1441468A (en) * | 1918-08-12 | 1923-01-09 | Wills Child Harold | Composite metal structure for internal-combustion engines and method of forming the same |
| US2046758A (en) * | 1932-11-28 | 1936-07-07 | Dewey And Almy Chem Comp | Aqueous dispersion of carbon black |
| US3067243A (en) * | 1959-07-28 | 1962-12-04 | Nopco Chem Co | Preparation of salts of naphthalene sulfonic acid-formaldehyde condensates |
| US3193575A (en) * | 1961-03-10 | 1965-07-06 | Basf Ag | Production of condensation products of naphthalenesulfonic acids and aldehydes |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4221639A (en) * | 1978-10-09 | 1980-09-09 | Kioritz Corporation | Aluminium alloy cylinder and manufacturing method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| BE706849A (cg-RX-API-DMAC7.html) | 1968-04-01 |
| DE1258697B (de) | 1968-01-11 |
| GB1061950A (en) | 1967-03-15 |
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